Electrolyte supported cell designed for longer life and higher power

ABSTRACT

A solid oxide fuel cell (SOFC) that includes an anode electrode, a cathode electrode and a solid oxide electrolyte having a fuel inlet riser opening and a fuel outlet riser opening. The electrolyte is located between the anode electrode and the cathode electrode. The SOFC also includes a ceramic support layer on the electrolyte. The ceramic support is layer located around the at least one of a periphery of the electrolyte or at least partially around perimeters of the fuel inlet and fuel outlet riser openings. The ceramic support layer comprises a multi-component material comprising yttria stabilized zirconia (YSZ) and alpha alumina.

The present application is divisional of U.S. patent application Ser. No. 13/586,552, filed Aug. 15, 2012, which is a continuation-in-part of U.S. patent application Ser. No. 13/268,233, filed Oct. 7, 2011, which is a divisional of U.S. patent application Ser. No. 12/292,151, filed Nov. 12, 2008 (now U.S. Pat. No. 8,067,129 issued Nov. 29, 2011), which claims benefit of U.S. Provisional Application Ser. Nos. 60/996,352 filed Nov. 13, 2007, 61/129,759 filed Jul. 17, 2008 and 61/129,882 filed Jul. 25, 2008, and application Ser. No. 13/268,233 claims benefit of priority of U.S. Provisional Application Ser. No. 61/539,045 filed Sep. 26, 2011, which are hereby incorporated by reference in their entirety.

BACKGROUND OF THE INVENTION

The present invention is generally directed to fuel cell components, and to solid oxide fuel cell materials in particular.

Fuel cells are electrochemical devices which can convert energy stored in fuels to electrical energy with high efficiencies. Electrolyzer cells are electrochemical devices which can use electrical energy to reduce a given material, such as water, to generate a fuel, such as hydrogen. The fuel and electrolyzer cells may comprise reversible cells which operate in both fuel cell and electrolysis mode.

In a high temperature fuel cell system, such as a solid oxide fuel cell (SOFC) system, an oxidizing flow is passed through the cathode side of the fuel cell, while a fuel flow is passed through the anode side of the fuel cell. The oxidizing flow is typically air, while the fuel flow can be a hydrocarbon fuel, such as methane, natural gas, propane, ethanol, or methanol. The fuel cell, operating at a typical temperature between 750° C. and 950° C., enables combination of the oxygen and free hydrogen, leaving surplus electrons behind. The excess electrons are routed back to the cathode side of the fuel cell through an electrical circuit completed between anode and cathode, resulting in an electrical current flow through the circuit.

Fuel cell stacks may be either internally or externally manifolded for fuel and air. In internally manifolded stacks, the fuel and air is distributed to each cell using risers contained within the stack. In other words, the gas flows through openings or holes in the supporting layer of each fuel cell, such as the electrolyte layer, and gas separator of each cell. In externally manifolded stacks, the stack is open on the fuel and air inlet and outlet sides, and the fuel and air are introduced and collected independently of the stack hardware. For example, the inlet and outlet fuel and air flow in separate channels between the stack and the manifold housing in which the stack is located.

Typically, SOFC are fabricated either as electrolyte supported, anode supported, or cathode supported, depending on which of the three functional components of the cell provides structural support. In planar electrolyte supported SOFC designs, the anode and cathode electrodes are painted as an ink onto the opposite surfaces of a planar ceramic electrolyte. However, weakness in structural integrity, particularly at or around the fuel inlet and outlet riser openings, might arise in these designs under certain loading conditions.

Ceramics are known to exhibit fracture before any plastic deformation can occur in response to an applied tensile load, such as during thermal cycling. Fracture in ceramics usually originates at preexisting defects, such as microcracks, internal pores, and grain corners. Fracture strength depends on the probability of the existence of a defect that is capable of initiating a crack. WILLIAM D. CALLISTER, JR., MATERIALS SCIENCE AND ENGINEERING, 5^(th) Ed. (1999), pages 407-409. For two ceramic samples containing identical defect densities, it is known that specimen size and volume influences fracture strength: “the larger the specimen, the greater this flaw existence probability, and the lower the fracture strength.” CALLSISTER, at 408.

SUMMARY OF THE INVENTION

An embodiment relates to a solid oxide fuel cell (SOFC) that includes an anode electrode, a cathode electrode and a solid oxide electrolyte having a fuel inlet riser opening and a fuel outlet riser opening. The electrolyte is located between the anode electrode and the cathode electrode. The SOFC also includes a ceramic support layer on the electrolyte. The ceramic support is layer located around the at least one of a periphery of the electrolyte or at least partially around perimeters of the fuel inlet and fuel outlet riser openings. The ceramic support layer comprises a multi-component material comprising stabilized zirconia and alumina, such as yttria stabilized zirconia (YSZ) and alpha alumina.

Another embodiment relates a method of making a solid oxide fuel cell (SOFC). The method includes providing a solid oxide electrolyte having an anode electrode on a first side and a cathode electrode on an opposing second side, the solid oxide electrolyte comprising a fuel inlet riser opening and a fuel outlet riser opening. The method also includes depositing a ceramic support layer on the electrolyte. The ceramic support layer is located around the at least one of a periphery of the electrolyte or at least partially around perimeters of the fuel inlet and fuel outlet riser openings. The ceramic support layer comprises a multi-component material comprising stabilized zirconia and alumina, such as yttria stabilized zirconia (YSZ) and alpha alumina.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates a side cross-sectional view of a SOFC of the embodiments of the invention, where the porous outer electrode layers and the middle electrolyte layer comprise the same material.

FIG. 2 illustrates a side cross-sectional view of a SOFC of the embodiments of the invention, where the porous outer electrode layers and the middle electrolyte layer comprise different materials.

FIG. 3 illustrates a side cross-sectional view of a SOFC of the embodiments of the invention, where an additional ceramic layer is located between each electrode and the electrolyte.

FIG. 4A illustrates a side cross-sectional view of a SOFC of the embodiments of the invention, where a non-continuous outer layer is added to the SOFC. FIG. 4B illustrates a top view of the SOFC of FIG. 4A.

FIGS. 4C and 5 illustrates a top view of the anode electrode of a SOFC of the embodiments of the invention.

FIG. 6 illustrates a side cross sectional view of a SOFC stack of an embodiment of the invention.

FIG. 7 illustrates a side cross-sectional view of a SOFC according to an embodiment of the invention in which one of the electrodes comprises a porous ceramic layer.

FIG. 8A illustrates a top view of a hole-reinforced electrolyte of a SOFC according to an embodiment of the invention.

FIG. 8B is a top view computational image of a simulated electrolyte undergoing a thermal load of about 600° C. to about 800° C.

FIGS. 8C-8H are schematic top views of an electrolyte containing various configurations of ceramic support layer according to embodiments of the invention.

FIGS. 81 and 8J illustrate respective side cross-sectional and top views of a rib-reinforced electrolyte of a SOFC according to another embodiment of the invention.

FIG. 9 is a histogram of frequency versus load to failure (in units of kg-F) illustrating the improvement in cell strength (load to failure) with the addition of ceramic reinforcing regions according to an embodiment.

FIG. 10 is a probability (Weibull) plot percent versus load to failure (in units of kg-F) illustrating the improvement in cell strength (load to failure) with the addition of ceramic reinforcing regions according to an embodiment.

FIG. 11 is a micrograph illustrating the microstructure of a support layer according to an embodiment.

DETAILED DESCRIPTION OF THE EMBODIMENTS

In one embodiment of the invention, only the electrode provides structural support for the cell. The anode and cathode electrodes comprise inks painted or screen printed onto the ceramic electrolyte, such as a stabilized zirconia and/or doped ceria, such as yttria stabilized zirconia (“YSZ”), scandia stabilized zirconia (“SCZ”), gadolinia doped ceria (“GDC”) and/or samaria doped ceria (“SDC”) electrolyte. In another embodiment of the invention, both electrodes and the electrolyte provide structural support for the fuel cell. This provides a higher strength for each cell and allows a thinner and/or larger footprint electrolyte while lowering the cost for electrolyte production. The dense electrolyte layer is located between two catalyst infiltrated electrode layers which have a higher porosity than the electrolyte layer. The electrolyte may be considered “non-porous” because the porosity of the electrolyte is lower than that of the electrodes and should be sufficiently low to prevent the electrode catalyst from infiltrating through the thickness of the electrolyte. However, it should be noted that as a ceramic material, the electrolyte contains a certain amount of porosity. While closed pores are allowed within the electrolyte because they do not have any connection with the surface, the amount of open porosity should be minimized. Preferably, the porosity limit is such that the permeability is low enough to avoid significant reaction of fuel and oxidizer without the flow of ions and that the permeability is low enough to maintain certain spatial separation between electrodes.

In one embodiment, the two outer electrode layers and the middle electrolyte layer are made of the same ceramic material, such as a stabilized zirconia. In another embodiment, the outer porous electrode layers are made of a different ceramic material from that of the electrolyte. The electrode layers may be made of the same or different ceramic material from each other. In either case, they are infiltrated with a different respective anode and cathode catalyst material. In yet another embodiment, ceramic interlayers and/or a non-continuous outer layer is added to the fuel cell to provide reinforcement, thereby providing additional mechanical strength to the fuel cell.

While the electrode catalysts are described above as being preferably produced by infiltration into a porous ceramic layer, the fuel cells may be made by any suitable methods. Furthermore, while stabilized zirconias, such as yttria, scandia and/or ceria stabilized zirconia, and doped cerias, such as samaria doped ceria, are preferred as the ceramic materials for the electrodes and/or electrolyte layers, other suitable ceramic materials may be used instead.

FIG. 1 illustrates a solid oxide fuel cell (SOFC) 1 according to a first embodiment of the invention. The fuel cell 1 includes a porous anode electrode 3, a dense solid oxide electrolyte 5 and a porous cathode electrode 7. In this embodiment, the electrode layers 3, 7 and the electrolyte layer 5 are made of the same ceramic material, such as a stabilized zirconia, such as yttria stabilized zirconia (“YSZ”), scandia stabilized zirconia (“SSZ”), scandia ceria stabilized zirconia (“SCSZ”) (which can also be referred to as scandium and cerium doped zirconia), or mixtures thereof. In one example, the electrolyte 5 and the electrodes 3, 7 may comprise YSZ or SSZ, such as 8 molar YSZ (i.e., 8 molar percent yttria/92 molar percent zirconia composite) or 8 molar percent SSZ; 10 molar or 11 molar percent SSZ can also be used. In another example, the electrolyte and the electrodes may comprise scandia ceria stabilized zirconia (SCSZ), such as 10 molar scandia 1 molar ceria stabilized zirconia. In another embodiment, the electrolyte may be a doped ceria material, such as gadolinia doped ceria (GDC). The anode and cathode catalysts are infiltrated into the porous electrodes 3, 7, respectively, with precursors that comprise salts or metal-organics dissolved in a solvent, or molten metal salts. The ratio of the salts, and hence the ratio of metal cations, in solution is such to form the desired catalyst phase upon heating and reactions of the components. The precursors can be heated in an oxidizing atmosphere in order to form oxides, or heated and reacted in a reducing atmosphere resulting in metal phases. In a reduced state, the anode electrode catalyst may comprise nickel, such as pure nickel or an alloy of nickel and another metal, such as copper. This catalyst is in a form of nickel oxide when it is in an oxidized state. Thus, the anode catalyst may be infiltrated as nickel oxide, and the anode electrode is then subsequently annealed in a reducing atmosphere prior to operation to reduce the nickel oxide to nickel. The cathode electrode catalyst may comprise an electrically conductive perovskite material, such as lanthanum strontium manganite (LSM). Other conductive perovskites having a general formula (La_(x)Sr_(1-x))(Mn_(y)A_(1-y))O₃ where A is Cr and/or Co, 0.6<x<0.9, 0≤y<0.4 or (La_(x)D_(1-x))(E_(y)G_(1-y))O₃ where D is Sr or Ca, and E and G are one or more of Fe, Co, Mn, and Cr (0.6<x<0.9, 0≤y<0.4), including LSCr, LSCo, etc., or noble metals, such as Pt, may also be used.

FIG. 2 illustrates a SOFC 11 according to a second embodiment of the invention. The cell 11 includes a porous anode electrode 3, a dense solid oxide electrolyte 5 and a porous cathode electrode 7. Electrodes 3 and 7 are made of a different material from that of the electrolyte 5. Electrodes 3 and 7 may be made from the same or different material as each other. Electrolyte 5 may be made of a highly ionically conductive material, such as SSZ, while electrodes 3 and 7 may be made of a higher strength, lower ionic conductivity material, such as YSZ. For example, 3 molar percent yttria YSZ (3YSZ) is used for the electrodes 3, 7. Alternatively, 4 molar percent yttria YSZ (4YSZ) is used to avoid the problems associated with phase transitions of 3YSZ. In general, YSZ compositions having more than 3 molar percent yttria, such as 3 to 10 molar percent yttria, for example 5 to 10 molar percent yttria (i.e., (ZrO₂)_(1-z)(Y₂O₃)_(z), where 0.03≤z≤0.1), may be used.

Preferably, the scandia stabilized zirconia for the electrolyte 5 has the following formula: [(ZrO₂)_(1-y)(CeO₂)]_(1-x)(Sc₂O₃)_(x), where 0.06≤x≤0.11 and 0≤y≤0.01. While a stoichiometric stabilized zirconia is described by the formula, a non-stoichiometric stabilized zirconia having more or less than two oxygen atoms for each metal atom may be used. For example, the electrolyte may comprise SCSZ having 1 molar percent ceria and 10 molar percent scandia (i.e., [(ZrO₂)_(1-y)(CeO₂)_(y)]_(1-x)(Sc₂O₃)_(x) where x=0.1 and y=0.01). The ceria in SCSZ may be substituted with other ceramic oxides. Thus, alternative scandia stabilized zirconias can be used, such as scandia yttria stabilized zirconia (“SYSZ”), which can also be referred to as scandium and yttrium doped zirconia, and scandia alumina stabilized zirconia (“SAlSZ”), which can also be referred to as scandium and aluminum doped zirconia. The yttria or alumina may comprise 1 molar percent or less in the scandia stabilized zirconia.

The number of layers in the SOFC need not be restricted to three. FIG. 3 illustrates a SOFC 21 according to the third embodiment. In this embodiment, one additional interlayer layer 4 is located between the electrolyte 5 and anode 3, and another interlayer 6 is located between the electrolyte 5 and cathode 7. If desired, only one of the layers 4, 6 may be used in the SOFC 21. Materials such as doped ceria, which can enhance redox stability of the cell and further reduce the usage of expensive materials, may be used to fabricate the interlayers 4, 6. Samaria, gadolinia or yttria doped ceria (in other words, the ceria may contain Sm, Gd and/or Y dopant element which forms an oxide upon incorporation into the ceria) may be used as the interlayer 4, 6 material. Preferably, the doped ceria phase composition comprises Ce_((1-x))A_(x)O₂, where A comprises at least one of Sm, Gd, or Y, and x is greater than 0.1 but less than 0.4. For example, x may range from 0.15 to 0.3 and may be equal to 0.2. The materials for the electrodes 3, 7 and electrolyte 5 may be the same as those described above with respect to the first and the second embodiments.

It is desirable that all layers 3, 4, 5, 6, 7 be as thin as possible. The thickness of the layers can be optimized to provide desired electrical and mechanical properties. For example, the middle electrolyte layer 5 should be at least 5 microns thick, such as about 25 to about 175 microns thick, such as about 25 to about 75 microns thick, while the thickness of the outer porous electrode layers 3, 7 can be between about 20 to about 100 microns. If the sintering properties of the three layers 3, 5, 7 are adjusted appropriately, then the thicknesses of the three layer cell can be asymmetric. The anode porous layer 3 may be thinner than the cathode layer 7 to allow high fuel utilization at the anode while the cathode can be kept thicker because air utilization is generally much less critical. For example, the anode layer 3 may be about 20 to about 50 microns thick while the cathode layer 7 may be about 50 to about 100 microns thick. For a five layer cell 21 shown in FIG. 3, the electrodes 3, 7 may be about 20 to about 100 microns thick, the electrolyte 5 may be 5 to 175 microns thick and the interlayers 4, 6 may be 5 to 20 microns thick. For example, the structure of cell 21 may comprise a 50 micron thick anode electrode 3 comprising 3YSZ or 4YSZ infiltrated with Ni or nickel oxide catalyst, a 10 micron thick doped ceria (such as SDC) interlayer 4, a 10 micron thick SSZ electrolyte 5, 10 micron thick doped ceria (such as SDC) interlayer 6, and a 50 micron thick cathode electrode 7 comprising 3YSZ or 4YSZ infiltrated with LSM or Pt catalyst. If desired, the anode electrode 3 may comprise a functionally graded electrode containing a first portion and a second portion, such that the first portion is located between the electrolyte 5 and the second portion. The first portion of the anode electrode contains a lower porosity and a lower ratio of the nickel containing catalyst to the ceramic matrix than the second portion of the anode electrode, as described in U.S. Provisional Patent Application Ser. No. 60/852,396 filed on Oct. 18, 2006, which is incorporated by reference in its entirety. For example, the first portion of the anode electrode may contain a porosity of 5-30 volume percent and a nickel phase content of 1 to 20 volume percent. The second portion of the anode electrode may contain a porosity of 31 to 60 volume percent and a nickel phase content of 21 to 60 volume percent. The first and second portions of the anode electrode may comprise two or more separate sublayers or the porosity and nickel content may be graded continuously or in steps along the anode electrode 3 thickness.

In another embodiment, a non-continuous outer or support layer 30 is added to the SOFC 31. One such embodiment is illustrated in FIGS. 4A and 4B, where the outer layer 30 comprises a sheet with hexagonal holes 32 exposing the underlying electrode 3 or 7. However, the holes 32 may have shapes other than hexagonal, such as rectangular, square, oval, circular, irregular, etc. The outer layer 30 may be 50 to 200 microns thick. The outer or support layer 30 may comprise any strong ceramic material, such as YSZ, SSZ or a doped ceria, which can be sintered and are compatible with the electrodes. The outer or support layer 30 may be located adjacent to the cathode electrode 7 or adjacent to the anode electrode 3. If desired, two support layers may be provided, one adjacent to the anode and the other one adjacent to the cathode electrode. As illustrated, the outer support layer 30 is added to the SOFC illustrated in FIG. 2. Alternatively, the outer support layer 30 may be added to the SOFC illustrated in FIG. 3.

FIG. 4B shows a top view of a cell 31 which is internally manifolded for fuel and externally manifolded for air. Hence, the cell contains internal fuel inlet 33 and outlet 34 riser openings. However, the cell 31 may be internally and/or externally manifolded for fuel and/or air as desired. The addition of the outer layer results in a reinforced structure, rendering additional mechanical strength to the cell and allowing the other layers to be sized to their electrochemical ideal thickness.

If the outer layer or layers 30 are located outside the electrochemically active area (referred to as a peripheral area), as shown in FIG. 4C, then even ionically non-conductive materials can be used for layer 30, such as a zirconia toughened alumina, which is an inexpensive, high-strength material. In FIGS. 4B and 4C, only the central or active portion 35 of the porous layer 3 is infiltrated with a catalyst to form the electrode of the cell. The peripheral areas, such as areas adjacent to the riser openings 33 and 34, may remain uninfiltrated with the catalyst. Alternatively, the entire plane of the porous layers may be infiltrated with a catalyst material.

If desired, a seal may be formed around the periphery of the porous layer(s) 3, 7 and/or around the riser openings (if present). As shown in FIG. 5, when the porous layer 3, 7 extends to the edge of the cell 41, the porous layer outside the active region near the edge or periphery of the cell may be filled with refractory, ceramic, glass, or a mixture thereof, such as a glass ceramic mixture to form a seal 42 to eliminate the potential problem arising from the interaction between the fuel and ambient air in or next to the pores. Alternatively, an edge seal may be used where the glass is allowed to flow over the thin outer edge of the electrolyte to form the seal. Alternatively, the nonporous middle electrolyte layer 5 can laterally extend past the porous layer(s) 3, 7 and be folded over the edge of the porous layer 3 or 7 to form the seal 42. Preferably, layer 5 is folded over the anode electrode layer 3 to form the seal. The folded seal may be used in combination with the filled pore type seal or with a conventional glass composite layer type of seal.

Fuel cell stacks are frequently built from a multiplicity of SOFC's in the form of planar elements, tubes, or other geometries. Fuel and air has to be provided to the electrochemically active surface, which can be large. As shown in FIG. 6, one component of a fuel cell stack is the so called gas flow separator (referred to as a gas flow separator plate in a planar stack) 9 that separates the individual cells in the stack. The gas flow separator plate separates fuel flowing to the fuel electrode (i.e. anode 3) of one cell in the stack from oxidant, such as air, flowing to the air electrode (i.e. cathode 7) of an adjacent cell in the stack. The fuel may be a hydrocarbon fuel, such as natural gas for internally reforming cells, or a reformed hydrocarbon fuel comprising hydrogen, water vapor, carbon monoxide and unreformed hydrocarbon fuel for externally reforming cells. The separator 9 contains gas flow passages or channels 8 between the ribs 10. Frequently, the gas flow separator plate 9 is also used as an interconnect which electrically connects the fuel electrode 3 of one cell to the air electrode 7 of the adjacent cell. In this case, the gas flow separator plate which functions as an interconnect is made of or contains electrically conductive material, such as a Cr—Fe alloy. An electrically conductive contact layer, such as a metal foil or thin sheet, perforated foil or thin sheet, mesh, or composite of these, may be provided between the anode electrode and the interconnect. A conductive ceramic paste, such as LSM paste, may be provided between the cathode electrode and the next adjacent interconnect of the stack. FIG. 6 shows that the lower SOFC 1 is located between two gas separator plates 9.

Furthermore, while FIG. 6 shows that the stack comprises a plurality of planar or plate shaped fuel cells, the fuel cells may have other configurations, such as tubular. Still further, while vertically oriented stacks are shown in FIG. 6, the fuel cells may be stacked horizontally or in any other suitable direction between vertical and horizontal. Additionally, the fuel cell stack may comprise a plurality of SOFCs illustrated in FIG. 3. That is, the fuel cell stack may comprise a plurality of SOFCs that include interlayers 4 and 6 between the electrodes 3, 7 and the electrolyte 5.

The term “fuel cell stack,” as used herein, means a plurality of stacked fuel cells which share a common fuel inlet and exhaust passages or risers. The “fuel cell stack,” as used herein, includes a distinct electrical entity which contains two end plates which are connected to power conditioning equipment and the power (i.e., electricity) output of the stack. Thus, in some configurations, the electrical power output from such a distinct electrical entity may be separately controlled from other stacks. The term “fuel cell stack” as used herein, also includes a part of the distinct electrical entity. For example, the stacks may share the same end plates. In this case, the stacks jointly comprise a distinct electrical entity. In this case, the electrical power output from both stacks cannot be separately controlled.

Any suitable ceramic fabrication method may be used for forming the SOFCs of the embodiments of the invention. For the ink-printed electrodes, the electrode inks (e.g., nickel and ceramic phase (e.g., doped ceria and/or stabilized zirconia) cermet inks) are applied to opposite sides of the electrolyte followed by sintering. The multi-layer structure of described SOFC may be fabricated laminate tape casting of the green ceramic (i.e., where the laminate tape contains the electrode matrix and electrolyte green ceramic). Alternatively, the SOFC can be created by multi layer tape casting. Calendering or roll compaction of multiple layers of tape allows further manipulation of the layer thickness. Other compacting methods, such as uniaxial or isostatic pressing of the tape cast layers, can also be used. The pressing may be performed with or without compatible organic adhesives. The electrode layers 3, 7 may contain pore former material(s) while the electrolyte 5 does not contain pore former material. Any suitable pore former material may be used, such as for example carbon (e.g., graphite, activated carbon, petroleum coke, carbon black or the like), starch (e.g., corn, barley, bean, potato, rice, tapioca, pea, sago palm, wheat, canna, or the like), and/or polymer (e.g., polybutylene, polymethylpentene, polyethylene (such as beads), polypropylene (such as beads), polystyrene, polyamides (nylons), epoxies, ABS, acrylics, polyesters (PET), or the like), as described in U.S. Published Application 2007/0006561, which is incorporated herein by reference. The pore former may comprise about 1 to about 25 weight percent of the green ceramic mixture which also includes the ceramic precursors (i.e., zirconia, scandia, yttria, ceria, etc.), a binder and a solvent. During a subsequent annealing step, such as a burn out, bake out or a sintering step, the pore former material(s) burn out and leave a porous electrode structure, while the middle electrolyte layer in the absence of pore formers becomes dense. Alternatively, the porous outer layers may be deposited after sintering or firing of the middle layer. The outer layers may be sintered or fired at a lower temperature than the middle layer. The outer layers or the interlayers can also be added by methods such as tape casting, screen printing, spin coating, etc. after sintering of the middle electrolyte layer; this addition allows sintering to take place at a lower temperature, thereby expanding the choice of materials.

The electrode and electrolyte layers are preferably sintered together to form a strong structural element. They can be sintered at any suitable temperature, such as a temperature between 1150 and 1400° C. in air. The electrodes are created by infiltrating the appropriate catalyst materials into the two outer porous electrode matrix layers 3, 7 either before and/or after the sintering step. The catalyst materials may be provided in a liquid or slurry form to the electrode matrix layers. Preferably, the infiltration step occurs after the sintering step. Infiltrated electrodes can be subjected to a bake out annealing step at a temperature of 600° C. or less, which is far below cell operating temperature and even further away from ceramic sintering temperatures, thereby avoiding the commonly observed weakening of SOFC when electrodes are applied externally and sintered. Also the reactivity of all materials involved is low at bake out temperature which avoids another common difficulty with conventionally fired electrodes which may form undesirable material phases.

FIG. 7 shows a SOFC 71 in which an electrode (anode or cathode) comprises a porous ceramic layer 73 and wherein the electrolyte comprises a ceramic thin film 75 having a porosity less than that of the porous ceramic layer 73. Together, the porous layer 73 and the thin film 75 comprise a ceramic structure 77. The ceramic structure 77 can be made of any suitable electrolyte material, such as scandia stabilized zirconia (SSZ). The porous layer 73 is preferably thicker than the thin film 75 and imparts structural support to the thin film 75. The porosity and thickness of the porous layer 73 can be tailored to meet the strength requirements of the SOFC 71. For example, the porous layer 73 has a thickness of about 100 μm to about 1000 μm, such as about 200 μm to about 500 μm. The thin film 75 has a thickness less than about 60 μm, such as about 10 μm to about 60 μm, preferably about 20 μm to about 50 μm.

To form an electrode, the porous layer 73 is infiltrated with either an anode material or a cathode material. For example, the porous layer 73 is infiltrated with nickel such that the porous layer comprises an anode electrode. Alternatively, the porous layer is infiltrated with an electrically conductive perovskite material, for example lanthanum strontium manganite (LSM), such that the porous layer 73 comprises a cathode electrode. Infiltration can be performed by depositing a solution of a precursor, such as a catalytic precursor, of the anode or cathode material into the pores of the porous layer 73.

The SOFC 71 also includes a second electrode 79 in contact with the thin film 75 of the structure 77. The second electrode 79 is preferably thinner than the film 75 or porous layer 73. For example, the second electrode 79 may be less than 40 μm thick, such as about 10-30 μm, preferably about 20 μm. The second electrode 79 can be formed either before or after infiltration is performed on the porous layer 73. If the porous layer 73 comprises an anode, then the second electrode 79 comprises a cathode. Alternatively, if the porous layer 73 comprises a cathode, then the second electrode 79 comprises an anode. The second electrode 79 can be deposited using convention methods, such as screen printing. After being deposited on the thin film 79, the second electrode 79 can be sintered either before or after the porous layer 73 is infiltrated with a solution. Sintering can be performed at a temperature of about 1150° C. to about 1400° C. Preferably, only a single sintering step is performed, such that the anode, cathode, and electrolyte are co-sintered at the same time.

An advantage of the SOFC 71 is that it minimizes the orange discoloration associated with degradation of SSZ electrolytes. Preferably, the electrolyte thin film 75 is sufficiently thin to minimize hydrogen diffusion within the electrolyte. Without wishing to be bound to any particular theory, it is believed that orange discoloration of SSZ electrolytes arises at least in part due to hydrogen diffusion and, thus, a reduction in the thickness of the electrolyte tends to decrease degradation and increase operating life. Aside from decreased degradation, the electrolyte thin film 75 of the SOFC 71 exhibits the additional advantage of reducing the ionic resistance of the electrolyte and thereby increasing cell performance.

FIG. 8A shows a fuel cell according to an alternative embodiment of the invention. As shown in FIG. 8A, a hole-reinforced electrolyte 171 comprises fuel inlet 133 and outlet 134 riser openings. The riser openings 133, 134 are located on an inactive region 177 of the electrolyte 171, which is located around the periphery of the anode electrode 103. In this embodiment, the anode electrode 103 may be an ink-printed electrode rather than the porous ceramic infiltrated with catalyst material of the previous embodiment or the anode electrode 103 may comprise the porous ceramic infiltrated with catalyst material. Each riser opening also includes ceramic reinforcing regions 173, 175 that are located at least partially around a circumference of each riser opening 133, 134. Preferably, the reinforcing regions 173, 175 provide improved mechanical properties (e.g., fracture strength, hardness, fatigue strength, fatigue, toughness) to the electrolyte 171 in the regions surrounding the riser openings 133, 134 where electrolyte failure is most likely to occur, thereby extending the life of the electrolyte 171. As shown in FIG. 8B, the areas of highest stress have been identified using finite element analysis (“FEA”) on a simulated electrolyte undergoing a thermal load of about 600° C. to about 800° C.

As shown in FIG. 8A, the reinforcing regions 173, 175 are located on the inactive region 177 of the electrolyte 171. Preferably, the thickness of the electrolyte plus the ceramic reinforcing region is thicker than that of the portion of the inactive region 177 not containing the ceramic reinforcing region and thicker than the portion of the electrolyte 171 covered by the anode 103. Preferably, reinforcing regions 173, 175 reinforce the electrolyte by being made of a tougher ceramic material than the electrolyte instead of or in addition to reinforcing the electrolyte by a difference in thickness. Thus, the difference in thickness can be greater than about 5 μm, such as about 5 μm to about 150 μm, including about 5 μm to about 125 μm, for example about 5 μm to about 20 μm, (e.g., about 10 μm to about 12 μm).

The reinforcing regions 173, 175 can be in the shape of a semicircle, horseshoe, crescent, or U-shaped. Preferably, the reinforcing regions 173, 175 formed on the anode side of the electrolyte do not form complete circles around the perimeters of the riser opening 133, 134, but are partially open (e.g., contain a channel 179 shown in FIGS. 8C-8E) to allow fuel from the anode side to enter and exit the inlet 133 and outlet 134 openings, respectively. The reinforcing regions 173, 175 can be located on either one or both sides of the electrolyte 171. In an embodiment, the reinforcing regions 173, 175 are located only on the anode (top) side of the electrolyte 171, while a seal (not shown) is located on the cathode (bottom) side entirely around the circumference of each riser opening to prevent mixing of fuel and air streams.

As shown in FIG. 8C, the reinforcing regions 173, 175 may be used in combination with the ceramic support layer 30 described above with respect to FIGS. 4A-4C. Layer 30 and regions 173, 175 may form a continuous shape around the circumference of the anode side of the electrolyte 5, 171. Alternatively, the regions 173, 175 may be formed on the anode side of the electrolyte 5, 171 while layer 30 may be omitted or while layer 30 is located on the cathode side of the electrolyte. The regions may have a curved or linear profile at the edge of the electrolyte, as shown in FIGS. 8D and 8E, respectively.

Alternatively, regions 173, 175 may be formed on the cathode side of the electrolyte 5, 171 as shown in FIGS. 8F-8H. In this case, the regions 173, 175 preferably completely encircle (e.g., cover the entire perimeter of) the riser openings 133, 134 and the channel 179 is omitted. Layer 30 and regions 173, 175 may form a continuous shape around the circumference of the cathode side of the electrolyte 5, 171, as shown in FIG. 8F. Alternatively, the regions 173, 175 may be formed on the cathode side of the electrolyte 5, 171 while layer 30 may be omitted or while layer 30 is located on the anode side of the electrolyte. The regions may have a curved or linear profile at the edge of the electrolyte, as shown in FIGS. 8G and 8H, respectively.

FIGS. 81 and 8J illustrate another embodiment. In this embodiment, the reinforcing regions comprise strengthening ribs 30 a. The ribs are formed on one or both of the anode or cathode sides of the electrolyte 5 surface prior forming the anode 3 and/or cathode 7 electrodes. As the electrolyte 5 gets thinner, the electrolyte 5 becomes more prone to damage. A thin electrolyte 5 can be effectively supported by providing strengthening ribs 30 a across the surface of the electrolyte 5 (i.e., in the active area of the cell) rather than only providing strengthening to regions 173, 175 adjacent to the fuel inlet and fuel outlet and around the periphery of the cell, as shown in FIG. 81. The ribs 30 a may be provided instead of regions 173, 175 as shown in FIG. 81 or the ribs 30 a may be provided in addition to regions 173, 175, as shown in FIG. 8J. The ribs 30 a may be located only in the active area of the electrolyte under the anode 3 electrode and/or the cathode 7 electrode, as shown in FIG. 81. Alternatively, the ribs 30 a may also extend through both the active and inactive regions such that they are exposed adjacent to the respective electrode (e.g., anode 3) in the inactive region, as shown in FIG. 8J. While four ribs are shown in FIGS. 81-8J, any number of ribs may be provided, such as 2-20 ribs.

The reinforcing regions 30 a, 173, 175 can be made in a variety of ways. For example, an additional layer of electrolyte material can be laminated and sintered on an electrolyte that has already been fired. The electrolyte is then sintered and solidified. Alternatively, a screen printing technique can be used to provide a ceramic paste (with or without reinforcing fibers and/or particles) onto the electrolyte. If reinforcing fibers or particles are incorporated into the paste, then the materials of the reinforcing phase can be similar or different than that of the base electrolyte substrate. Preferably, the material of the reinforcing phase has a similar coefficient of thermal expansion as that of the base electrolyte substrate, such that cracking due to thermal cycling is minimized. The electrolyte on which the paste is deposited can either be a fired electrolyte or a green tape that has not yet been fired. The green tape can contain the electrolyte, anode, and cathode. In the case of a green tape, the ceramic paste can be co-sintered together with the green tape in order to reduce the number of firing steps used during fuel cell fabrication.

In an embodiment, the ceramic support (e.g., at least one of the support layer 30 and/or the reinforcing regions 30 a, 173, 175) comprises a multi-component ceramic material comprising a stabilized zirconia and alumina. Preferably, the material comprises yttria stabilized zirconia (YSZ) and alpha alumina (e.g., hexagonal crystal structure phase of alumina). The multi-component material may have a weight ratio of YSZ to alpha alumina of 2-5:1. That is the ratio of YSZ to alpha alumina may vary from 2:1 to 5:1. For example, the weight ratio of YSZ to alpha alumina may be 3:1. In an embodiment, the YSZ has less than 5 atomic percent yttria. For example, the YSZ may have approximately 1-5 atomic %, yttria, such as 2-4 atomic percent, such as 3 atomic percent yttria (3YSZ). However, stabilized zirconias other than YSZ, such as SSZ, may be used instead of or in combination with YSZ. If desired, the stabilized zirconia powder particles may comprise a core/shell structure having a SSZ core and a YSZ shell, or a YSZ core and a SSZ shell.

In an embodiment, the electrolyte 5, 171 is made of scandia stabilized zirconia (SSZ). In this embodiment, the support layer 30 and/or the reinforcing regions 30 a, 173, 175 have higher fracture toughness than the electrolyte. The higher fracture toughness of the reinforcing regions 173, 175 reduces the formation of cracks in critical regions, such as the fuel inlet 133 and outlet 134 riser openings or the periphery of the electrolyte. The reinforcing regions 173, 175 may fully or partially surround the perimeters of the fuel inlet 133 and outlet 134 riser openings or the periphery of the electrolyte, as shown in FIGS. 8C-8H. Since the multi-component stabilized zirconia (e.g., SSZ and/or YSZ) and alumina (e.g., alpha alumina) of the reinforcing regions 173, 175 is tougher than the stabilized zirconia (e.g., SSZ) of the electrolyte, the regions 173, 175 reinforce the electrolyte by being made of a tougher ceramic material than the electrolyte. If desired, the electrolyte powder particles that are eventually pressed and sintered to form the electrolyte may comprise a core/shell structure having a SSZ core and a YSZ shell, or a YSZ core and a SSZ shell to form a composite stabilized zirconia electrolyte.

In an embodiment, the multi-component ceramic material has a coefficient of thermal expansion (CTE) within 5% of (e.g., 0-5% different from) the CTE of the material of the electrolyte 5, 171. In this manner, the generation of thermal stresses due to thermal cycling (heating and cooling) of the SOFC can be reduced.

Both the material components and the grain structure/microstructure affect the fracture toughness of a material. In an embodiment, the reinforcing regions 30 a, 173, 175 have an average grain size of less than 5 microns, such as less than 1 micron, for example 50 to 500 nm. Further, the reinforcing regions 30 a, 173, 175 need not be located on a particular side of the electrolyte to provide reinforcement. The reinforcing regions 30 a, 173, 175 may be located, for example, on an anode side of the electrolyte, the cathode side of the electrolyte or both sides of the electrolyte, as described above.

In an embodiment, the support layer 30 and/or the reinforcing regions 30 a, 173, 175 are made via a powder process. The process includes mixing a stabilized zirconia and alumina powders in a desired ratio (e.g., 2-5 to 1 weight ratio) to form a powder mixture. The powders preferably have an average particle size below 1 micron, such as 50-500 nm. An optional organic binder may be added to the powder mixture to form a strengthening ink (e.g., the ink includes 20-30 wt %, such as 24-26 wt % binder and remainder stabilized zirconia and alumina). The ink (e.g., the binder containing powder mixture) is deposited on the electrolyte in a designed pattern (e.g., a pattern shown in FIGS. 8A, 8C-8J or another pattern) and then sintered to burn out the binder. Alternatively, rather than providing a mixture of separate zirconia and alumina powders where each particle is made of either the zirconia or the alumina, the powder may comprise particles that are already made of a combination of stabilized zirconia and alumina in the desired ratio (e.g., each particle is made of an oxide of zirconium, aluminum and a stabilizing metal, such as yttrium or scandium).

The electrolyte 5, 171 containing layer 30 and/or the reinforcing regions 30 a, 173, 175 may be sintered at temperatures above 1150 C, such as 1200-1300 C, to burn out the organic binder and sinter the ceramic particles into a polycrystalline support layer (e.g., 30 and/or 30 a, 173, 175). If desired, a sintering aid (e.g., transition base metal salt and/or alkali or alkali earth metals (metal from Group 1 or 2 of the Periodic Table)) may be added to the particles to lower the sintering temperature. The process may also include hot isostatically or uniaxially pressing the ceramic multi-component material before, after or during the step of sintering. The anode electrode 3 and the cathode electrode 7 may be deposited on the electrolyte before or after the layer 30 and/or the reinforcing regions 173, 175. The electrodes may be fired/sintered together or separately from each other. One or both electrodes may be fired/sintered together or separately from the ceramic support layer (e.g., layer 30 and/or regions 173, 175).

FIGS. 9 and 10 illustrate the improvement in fracture properties of a reinforced solid oxide fuel cell (labeled “R”) according to an embodiment relative to an unreinforced SOFC (labeled “UR”). FIG. 9 is a histogram which illustrates the frequency of failure as a function of the load to failure in units of kg-F. The data is obtained by placing a SSZ electrolyte with and without reinforcing regions 173, 175 into bending mode and measuring load to breaking of the electrolyte.

FIG. 9 also shows statistical curves based on the histogram data. As can be seen in FIG. 9, the addition of reinforcing regions 173, 175 increases the average load to failure of the SOFC. That is, a reinforced cell can withstand higher loads before cracking than an unreinforced cell. This can also be seen in FIG. 10 which illustrates the cumulative probability of cell failure as a function of load. As shown in FIG. 10, the addition of reinforcing regions 173, 175 shifts the probability curve to towards higher loads. That is, a higher percentage of reinforced cells will withstand a given force (e.g., will have fewer failures) than unreinforced cells. A stack (e.g., as shown in FIG. 6) of reinforced cells with reinforcing regions 173, 175 has an about 10-15% increase in yield compared to the yield of a similar SOFC stack in which the SOFCs lack the reinforcing region.

FIG. 11 is a micrograph illustrating the microstructure of a reinforcing region 173, 175 on a SSZ electrolyte 5, 171 according to an embodiment. In this embodiment, the reinforcing region includes alpha alumina 173 a (dark material) and 3YSZ (173 b) (light colored material) in a 1:3 weight ratio. As shown in the micrograph, this material can be sintered to a high density (e.g., low porosity). Further, the material provides excellent adhesion to the electrolyte layer as evidenced by the smooth, continuous boundary.

The foregoing description of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed, and modifications and variations are possible in light of the above teachings or may be acquired from practice of the invention. The description was chosen in order to explain the principles of the invention and its practical application. It is intended that the scope of the invention be defined by the claims appended hereto, and their equivalents. 

What is claimed is:
 1. A method of making a solid oxide fuel cell (SOFC) comprising: providing a solid oxide electrolyte having a thickness of 25-175 μm and comprising an active region and an inactive region surrounding the active region, the inactive region comprising a fuel inlet riser opening and a fuel outlet riser opening; forming an anode electrode on a first side of the electrolyte in the active region, and forming a cathode electrode on a second side of the electrolyte in the active region; and depositing a ceramic support layer on the electrolyte, the-ceramic support layer located around at least one of a periphery of the electrolyte or at least partially around perimeters of the fuel inlet and fuel outlet riser openings, wherein the ceramic support layer comprises a multi-component material comprising a stabilized zirconia and alumina.
 2. The method claim 1, wherein the stabilized zirconia comprises yttria stabilized zirconia (YSZ) and the alumina comprises alpha alumina.
 3. The method of claim 2, wherein a weight ratio of the YSZ to the alpha alumina is 2-5:1.
 4. The method of claim 3, wherein the YSZ has less than 5 atomic % yttria.
 5. The method of claim 4, wherein, the YSZ has less than 3% yttria, a weight ratio of the YSZ to the alpha alumina is 3:1, and the ceramic support layer is located at least partially around perimeters of the fuel inlet and fuel outlet riser openings in the electrolyte to form electrolyte reinforcing regions.
 6. The method of claim 1, wherein depositing a ceramic support layer comprises depositing an ink comprising stabilized zirconia and alumina ceramic particles with an average particle size less than 1 micron and an organic binder followed by sintering the stabilized zirconia and alumina ceramic particles.
 7. The method of claim 6, further comprising sintering the ceramic support layer at temperatures above 1150 C to burn out the binder and sinter ceramic particles into a polycrystalline support layer.
 8. The method of claim 7, further comprising hot isostatically or uniaxially pressing the ceramic support layer before, after or during the step of sintering.
 9. The method of claim 1, wherein the ceramic support layer surrounds the active region of the electrolyte.
 10. The method of claim 1, wherein substantially all of the ceramic support layer is disposed outside of the active region.
 11. The method of claim 10, further comprising firing the anode and cathode electrodes together with the ceramic support layer or separately from the ceramic support layer.
 12. The method of claim 1, wherein: the ceramic support layer is located on the inactive region of the electrolyte; and a combined thickness of the electrolyte and the ceramic support layer is thicker than a thickness of the active region and thicker than a thickness of the inactive region that does not contain ceramic support layer.
 13. The method of claim 12, wherein the combined thickness of the electrolyte and the ceramic support layer is about 5 μm to about 20 μm thicker than the thickness of the active region and about 5 μm to about 20 μm thicker than the thickness of the inactive region that does not contain the ceramic reinforcing region.
 14. A method of making a solid oxide fuel cell (SOFC) comprising: providing a solid oxide electrolyte having a thinckness of 25-175 μm and comprising an active region and an inactive region surrounding the active region, the inactive region comprising a fuel inlet riser opening and a fuel outlet riser opening; forming an anode electrode on a first side of the electrolyte and a cathode electrode on a second side of the electrolyte; and depositing a stabilized zirconia and alumina ceramic support layer on the inactive region such that the ceramic support layer at least partially surrounds the fuel inlet and fuel outlet riser openings, wherein substantially all of the ceramic support layer is disposed outside of the active region.
 15. The method of claim 14, wherein the ceramic support layer is disposed on the first side of the electrolyte and comprises channels leading to the anode electrode.
 16. The method of claim 14, wherein the ceramic support layer completely surrounds the anode electrode.
 17. The method of claim 14, wherein the ceramic support layer is disposed on the second side of the electrolyte and completely surrounds the fuel inlet and fuel outlet riser openings.
 18. The method of claim 17, wherein the ceramic support layer completely surrounds the cathode electrode.
 19. The method of claim 14, wherein depositing a stabilized zirconia and alumina ceramic support layer comprises depositing an ink comprising stabilized zirconia powder particles and alumina powders particles and an organic binder, followed by sintering the stabilized zirconia and alumina powder particles.
 20. The method of claim 14, wherein depositing a stabilized zirconia and alumina ceramic support layer comprises depositing an ink comprising powder particles made of combination of stabilized zirconia and alumina, and an organic binder, followed by sintering the combination stabilized zirconia and alumina powder particles. 